The present invention provides the compounds having the generic structure: ##STR5## wherein R.sub.1 is hydrogen or ethylidene having the structure: EQU [H.sub.3 C--C.dbd.
and R.sub.2 is hydrogen or no group; wherein one of the wavy lines is a carbon-carbon double bond and the other of the wavy lines is a carbon-carbon single bond; with the proviso that when the .DELTA..sup.2,3 bond is a carbon-carbon double bond, R.sub.2 is hydrogen and R.sub.2 and the moiety: ##STR6## are so juxtaposed that the molecule having the structure: ##STR7## exists in two different isomeric forms; a "+" and a "-" form. Such compounds are provided by a novel process of our invention described hereinafter which gives rise to novel intermediates including the compounds having the generic structure: ##STR8## wherein X is chloro, bromo or iodo, R.sub.3 is hydrogen or no group; wherein one of the wavy lines is a carbon-carbon double bond and the other of the wavy lines is a carbon-carbon single bond; with the proviso that when the .DELTA..sup.2,3 bond is a carbon-carbon double bond, then R.sub.3 is hydrogen and R.sub.3 and the moiety: ##STR9## are so juxtaposed that the molecule having the structure: ##STR10## exists in two different forms; a "+" and a "-" form.
Compounds produced using the processes of our invention including a number of the intermediates produced are useful for their organoleptic properties in perfumes, perfumed articles, foodstuffs, foodstuff flavoring compositions, chewing gums, toothpastes, medicinal products, tobaccos, tobacco flavoring compositions, substitute tobaccos and substitute tobacco flavoring compositions.
In the perfumery art, there is a considerable need for substituents having sweet, floral, fruity, rose-like, minty/camphoraceous aromas with floral, hay-like, musty backgrounds and tobacco nuances. Specifically described herein are materials having such organoleptic profiles but which do not discolor with age. Such fragrance materials have a wide utilization in the presence of these perfume compounds. A limited amount of such materials that give rise to these properties is available from natural sources but the natural materials are subject to wide variations in quality, or are expensive, and/or often in critically short supply. This particularly holds true for the use of alpha damascone, beta damascone and mixtures of alpha damascone and beta damascone.
In addition, there is a continuing search for food flavor compositions which can vary, fortify, modify, enhance, augment or otherwise improve the flavor and/or aroma of foodstuffs, medicinal products, toothpastes, and chewing gums. To be satisfactory, such compositions should be stable, non-toxic and blendable with other ingredients to provide their own unique flavor and aroma nuances without detracting from the co-ingredients of the formulations in which they are used. Preferably, such compositions should be naturally occurring or present in natural foodstuffs so that their ingestible safety can be readily recognized. These materials should be capable of being synthesized in a simple and economical manner. The need for safe flavors in the mint, lemon and tropical fruit flavor area is well known particularly in the ice cream and yogurt flavor areas. More specifically, there is a need for the development of non-toxic materials which can replace natural materials not readily available, having herbaceous, earthy, patchouli-like, damascenone-like, lemony and minty aroma and flavor characteristics.
In tobacco flavoring art (pertaining to tobaccos and substitute tobaccos) there is a considerable need for substituents having musty-floral, slightly sweet, fruity and damascenone-like aromas and tastes in tobacco prior to smoking and sweet, Virginia tobacco-like notes on smoking in both the main stream and the side stream. Specifically described herein are materials having such an organoleptic profile but which do not discolor with age.
The instant invention provides the foregoing, which the prior art has heretofore fails to provide. Furthermore, nothing in the prior art shows the unexpected, unobvious and advantageous value of the compounds having the structures: ##STR11## for their organoleptic properties.
The compounds having the structures: ##STR12## are disclosed in the prior art at: Chem. Abstracts, Vol. 78, No. 110669t (Abstracts of J. Org. Chem. 1973, 38 [5], 894-6);
Chem. Abstracts, Vol. 80, No. 27395w (Abstracts of J. Chem. Soc., Chem. Communications 1973 [19], 7842; and at PA1 Chem. Abstracts, Vol. 79, No. 42041a (Abstract of German Offlegungschrift No. 2,244,680). German Offlegungschrift 2,244,680 includes a genus which could read on the compound having the structure: ##STR13## but no specific disclosure thereof is made in said German Offlegungschrift. PA1 Chem. Abstracts 54:345f (U.S. Pat. No. 2,853,520); PA1 Chem. Abstracts, Vol. 50, 8540h (Abstract of Chanley, et al, J. Am. Chem. Soc. 77, 6056-7 [1955]); PA1 Chem. Abstracts 50:15442b (Abstract of Landor, J. Chem. Soc., 1956, 1015-1019); PA1 Chem. Abstracts, Vol. 48, 13644i (Abstract of Newman, J. Am. Chem. Soc., 75, 4740-2 [1953]); and PA1 Chem. Abstracts, Vol. 47:1098h (Abstract of Henbest, et al, J. Am. Chem. Soc., 1952, 1150-4)
In addition, the preparations of these compounds have been carried out in a rather complex manner as is shown in:
Nothing in the prior art, however, discloses a process whereby a compound having the structure: ##STR14## can be hydrogenated using a Lindlar catalyst to form compounds having the structures: ##STR15##
Another group of products produced as a result of using the processes of our invention are alpha-damascone and beta-damascones having the structures: ##STR16## These compounds are shown to be useful for their organoleptic properties by Kovats at Chem. Abstracts, Vol. 74, page 76564k ("Cycloaliphatic Unsaturated Ketones for Use as Perfumes").
Mixtures, presumably predominantly cis,trans-.DELTA.-damascone with minor amounts of trans, trans-.DELTA.-damascone have been produced by Ayyar, Cookson and Kagi as set forth in J. Chem. Soc., Perkin Trans. 1, 1975 (17) 1727-36 [Title: "Synthesis of .delta.-Damascone[trans-1-(2,6,6-Trimethylcyclohex-3-enyl)but-2-en-1-one] and .beta.-Damascenone [trans-1-(2,6,6-Trimethylcyclohexa-1,3-dienyl)but-2-en-1-one]"]. The reaction sequence of the Ayyar synthesis of compositions presumed to be predominantly cis, trans-.DELTA.-damascone with minor amounts of trans, trans-.DELTA.-damascone is as follows: ##STR17## wherein the wavy line is representative of a "cis" or "trans" configuration of the methyl moiety with respect to the acetyl or crotonoyl moiety, both of which are bonded to the cyclohexenyl moiety, the "cis" isomer presumably being the major isomer and the "trans" isomer presumably being the minor isomer in this reaction sequence.
Nothing in the prior art, however, teaches the usefullness of the processes of our invention or the usefullness of the compounds having the structures: ##STR18## for their organoleptic properties.